CN108249550B - Preparation method of multi-effect remediation material for remedying organic polluted underground water - Google Patents
Preparation method of multi-effect remediation material for remedying organic polluted underground water Download PDFInfo
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Abstract
The invention discloses a preparation method of a multi-effect repairing material for repairing organic polluted underground water, wherein the repairing material is prepared by compounding an environment repairing material, an oxygen release material, an additive, biochar, modified ultramicro zinc oxide and a pH buffering agent through a certain process. The multi-effect repair material prepared by the invention has stable property, large surface area and better adsorption and catalytic oxidation activity; the oxygen release duration is long, the release efficiency is high, and the sustainability of the groundwater bioremediation effect can be ensured; the multifunctional groundwater remediation agent realizes the multi-effect synergy of adsorption, chemical oxidation, catalytic oxidation and bioremediation, overcomes the problems of single treatment function, poor regulation and control of treatment effect, secondary pollution and the like of the existing groundwater remediation agent, and is a multifunctional groundwater remediation agent which accords with the green sustainable remediation concept.
Description
Technical Field
The invention belongs to the technical field of groundwater remediation, and particularly relates to a preparation method of a multi-effect remediation material for remediating organically-polluted groundwater.
Background
Groundwater is an important component of fresh water resources and plays a significant role in the development of the human society. However, the random stacking of industrial wastes, the large use of pesticides and fertilizers, and the leakage in the processes of oil exploitation, transportation, loading, unloading, storage, processing and use all cause serious water and soil pollution and great threat to public health. With the rapid development of industrial and agricultural in China, more and more organic chemical pollutants enter the natural environment, and permeate into the soil environment along with surface runoff, and further enter the underground water environment, so that the quality of underground water in China is gradually deteriorated, the polluted area of the underground water is continuously enlarged, the underground water tends to evolve from point to surface and diffuse from local to area, the pollution degree is intensified, and the harm is gradually serious. The main source of organic pollution of groundwater is the leakage of petroleum and petroleum products. Petroleum Hydrocarbons (PHCs) are complex compounds composed of hundreds of compounds, are complex in composition, and bioaccumulative, and can be retained in the environment for a long period of time. Once groundwater is contaminated with petroleum hydrocarbons, it is generally difficult to restore water quality in the natural state for decades.
Remediation methods for organically-polluted groundwater generally include ex-situ remediation and in-situ remediation methods. The ex-situ remediation method mainly refers to a traditional treatment mode of extracting polluted underground water and then performing ex-situ treatment. The method has larger disturbance to the underground water, is easy to form the diffusion of pollutants, and is difficult to achieve the remediation target. The efficient in-situ remediation technology is gradually becoming a new direction for remediation and treatment of organic pollution of underground water. For in situ remediation, adding corresponding remediation materials (agents), such as an oxidant for directly oxidizing organic pollutants and an oxygen release agent for enhancing biological treatment, is the key to the development of in situ remediation. The existing repair material applied to in-situ repair has single function, the activity and efficiency of repair are to be improved urgently, and the repair material is high in price, large in using amount, slow in reaction, easy to form secondary pollution and the like. Research on repair materials has become a hotspot and difficulty of groundwater repair research at home and abroad.
The invention discloses a preparation method of a multi-effect repair material for repairing organic polluted underground water, which is used for preparing a composite repair material with multiple repair functions of oxidation, adsorption, oxygen release, bioremediation and the like, wherein the oxygen release component can provide a long-term and efficient solid oxygen supply source for repairing the polluted underground water and promote the bioremediation of the underground water; meanwhile, the natural potassium manganese ore material with nano-aperture has good adsorption and oxidation capacity on organic pollutants; the modified nano zinc oxide has the catalytic capability on the oxidation reaction of organic pollutants and can further strengthen the treatment process of the organic pollutants.
Disclosure of Invention
The invention aims to provide a preparation method of a multi-effect repair material for repairing organic polluted underground water, which can realize sustainable repair of underground water pollution and improve the environmental treatment efficiency.
In order to achieve the purpose, the technical scheme of the invention is as follows: a preparation method of a multi-effect remediation material for remediating organically-polluted underground water is characterized by comprising the following steps:
A. after ball milling, natural potassium manganese ore is put into a ball mill and screened to obtain natural potassium manganese ore particles with the particle size of 80-150 meshes, pore channel structures and the pore diameter of 0.46-50.00 nm;
B. preparing biochar: cleaning biomass, soaking the biomass in a KOH solution, taking out the biomass, cleaning, air-drying the biomass, drying the biomass in an oven, performing medium-temperature anoxic pyrolysis on the dried biomass to obtain biochar, and crushing the biochar into 50-80 meshes for sealing for later use;
C. preparing modified ultramicro zinc oxide:
putting zinc acetate and sodium acetate into a ball mill for ball milling, and transferring the powder into a crucible when the powder is viscous and transparent;
secondly, moving the crucible into a microwave oven for oxygen-limited heating, and naturally cooling in inert gas to obtain ultrafine zinc oxide particles;
thirdly, adding a copper source into the ultrafine zinc oxide particles, grinding the ultrafine zinc oxide particles by using a mortar, then putting the ultrafine zinc oxide particles into a microwave oven again for oxygen-limited heating, and naturally cooling the ultrafine zinc oxide particles in inert gas;
adding partial hydrogenated vegetable oil and isobutanol, stirring uniformly, washing with deionized water, drying in vacuum, and ball-milling to obtain modified ultrafine zinc oxide particles;
D. firstly, adsorbing an oxygen release material on the surface of the biochar, and then mixing and pressing the biochar with natural potassium manganese ore particles, an additive, modified ultrafine zinc oxide particles and a pH buffering agent to form a flaky mixture;
E. calcining the flaky mixture for 4-6 h at 150-200 ℃ under the protection of inert atmosphere, cooling under the protection of inert gas, and crushing to obtain the multi-effect composite repairing material.
Preferably, in the step D, the multi-effect composite repairing material for repairing the organic polluted groundwater comprises the following components in parts by weight: 10-35 parts of natural potassium manganese ore particles, 20-45 parts of oxygen release materials, 5-18 parts of additives, 10-25 parts of biochar, 5-20 parts of modified ultrafine zinc oxide particles and 15-30 parts of pH buffering agents.
Further, the natural potassium manganese ore in the step A adopts [ MnO ]6]Forming 2 x 2 type natural potassium manganese ore by double-chain common-angle oxygen ejection formed by octahedron common edges, and crushing and screening to obtain the natural potassium manganese ore with nano-aperture.
Further, the oxygen release material comprises one or any combination of two of the two base materials of calcium peroxide and magnesium peroxide.
Furthermore, the additive is one or any combination of several of natural sodium bentonite, zeolite or calcium carbonate.
Furthermore, the biomass is one or any combination of several of crop straws, peanut shells, shaddock peels and coconut shells.
Further, the pH buffering agent is any combination of two or more of potassium dihydrogen phosphate, potassium hydrogen phosphate, diammonium hydrogen phosphate and ammonium sulfate.
The prepared multi-effect repair material can be used for repairing underground water polluted by organic matters and can also be used for repairing surface water polluted by organic matters.
The invention creatively provides a preparation method of a multi-effect composite repair material for repairing organic polluted underground water, namely 'adsorption + chemical oxidation + catalytic oxidation + biological repair'. The repairing material is compounded by an environment repairing material, an oxygen release material, an additive, biochar, modified ultramicro zinc oxide and a pH buffering agent. The natural potassium manganese ore as the environment repairing material has good environmental attributes such as surface repairing, pore channel effect and nano effect due to the special crystal structure and chemical characteristics, and can adsorb and oxidize organic pollutants; the oxygen release material can provide a solid oxygen supply source to promote the biological remediation of underground water; the additive, such as natural sodium bentonite, has adsorption performance, is a layered structure formed by natural octahedral sheets, a good chemical reaction site is formed between layers, and the additive can slow down the contact of an oxygen release material and water after absorbing water and expanding, and prolong the oxygen release time; the biochar has adsorption performance, plays a role in dispersing, and inhibits powder agglomeration; the modified ultramicro oxidizability can catalyze and accelerate the degradation of organic matters; the pH buffering agent can inhibit the alkaline environment generated by the oxygen release functional material, buffer the pH value, maintain the proper environment of the microorganism and provide nutrition for the microorganism. The multi-effect repair material prepared by the invention has stable property, large surface area and better adsorption and catalytic oxidation activity; the oxygen release duration is long, the release efficiency is high, and the sustainability of the groundwater bioremediation effect can be ensured; the multifunctional groundwater remediation agent realizes the multi-effect synergy of adsorption, chemical oxidation, catalytic oxidation and bioremediation, overcomes the problems of single treatment function, poor regulation and control of treatment effect, secondary pollution and the like of the existing groundwater remediation agent, and is a multifunctional groundwater remediation agent which accords with the green sustainable remediation concept.
Compared with the prior art, the invention has the following advantages:
(1) the existing repair material has single function, and the activity and efficiency of repair are to be improved urgently. The invention can realize multiple repair functions of adsorption (enrichment), catalysis/chemical oxidation, oxygen supply and biological repair of organic polluted groundwater by optimizing the combination of a plurality of different repair functional materials, strengthen the repair process and improve the repair effect.
(2) The multi-effect repairing material contains the potassium manganese ore component with the nano aperture, belongs to a natural material, is low in cost and simple and convenient to prepare, has the functions of thermal stability, adsorption performance, nano effect, catalytic oxidation and the like, and has a good repairing effect on underground water.
(3) The oxygen release material in the multi-effect repair material solves the problem that the prior oxygen release agent is difficult to control the oxygen release rate and causes the waste of available oxygen in an oxygen release compound by compounding calcium peroxide or magnesium peroxide with an additive and biochar; and the addition of a pH buffer can improve the increase in groundwater pH due to oxygen release from calcium peroxide. The composite material can improve the oxygen release efficiency and buffer the pH change at the same time, and can effectively strengthen the biological treatment process of underground water.
(4) The preparation method of the multi-effect restoration material provided by the invention has the advantages that the needed raw materials are rich and the price is low, the used materials are mostly natural materials, the potential secondary pollution can not be caused when the prepared multi-effect restoration material is introduced into the soil and underground water environment, and the green sustainable restoration concept is met.
Drawings
FIG. 1 is a preparation process diagram of the multi-effect repair material of the invention.
Fig. 2 is a diagram of the change of the multiple-effect repair material-aqueous solution system DO.
FIG. 3 is a diagram of the pH change of the multi-effect repair material-aqueous solution system.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
A preparation method of a multi-effect repairing material for repairing organic polluted underground water is characterized in that the preparation method of the multi-effect repairing material comprises the following steps:
A. putting the natural potassium manganese ore into a ball mill for ball milling for 8-12 h, and screening to obtain natural potassium manganese ore particles with the particle size of 80-150 meshes, pore channel structures and the pore diameter of 0.46-50.00 nm;
B. preparing biochar: cleaning biomass, soaking the biomass in 3.5-5.5 mg g-1 KOH solution for 30 h, taking out, cleaning, air-drying, putting the biomass in an oven at 50-60 ℃ for overnight drying, carrying out medium-temperature anoxic pyrolysis on the dried biomass for 3-8 h to obtain biochar, and crushing the biochar into 50-80 meshes for sealing for later use;
C. preparing modified ultramicro zinc oxide:
putting zinc acetate and sodium acetate into a ball mill, carrying out ball milling for 15 min, and transferring the powder into a crucible after the powder is viscous and transparent (preferably, the mol ratio of the zinc acetate to the sodium acetate is 1: 1-1.4);
secondly, moving the crucible into a microwave oven, heating for 20 min in a limited oxygen mode, and naturally cooling in inert gas to obtain ultrafine zinc oxide particles;
thirdly, adding a copper source (mass ratio is 1: 0.08-0.2) into the ultrafine zinc oxide particles, grinding for 10 min by using a mortar, putting into a microwave oven again, performing oxygen-limited heating for 10 min, and naturally cooling in inert gas;
fourthly, adding a certain amount of partially hydrogenated vegetable oil and isobutanol (preferably, the volume ratio of the partially hydrogenated vegetable oil to the isobutanol is 3: 2), stirring uniformly at a certain temperature, washing with deionized water, drying in vacuum at 80-100 ℃, and ball-milling to obtain the modified ultrafine zinc oxide particles.
D. Firstly, adsorbing an oxygen release material on the surface of the biochar, then mixing the biochar with an environment repairing material, an additive, modified ultramicro zinc oxide particles and a pH buffering agent, and pressing the mixture into a sheet shape;
E. calcining the flaky mixture for 4-6 h at 150-200 ℃ under the protection of inert atmosphere, cooling under the protection of inert gas, and crushing to obtain the multi-effect repair material.
The multi-effect repair material comprises the following components in parts by weight, based on 100 parts by weight: 10-35 parts of natural potassium manganese ore particles, 20-45 parts of oxygen release materials, 5-18 parts of additives, 10-25 parts of biochar, 5-20 parts of modified ultrafine zinc oxide and 15-30 parts of pH buffering agents.
Further, the natural potassium manganese ore particles are [ MnO ]6]Forming 2 x 2 type natural potassium manganese ore by double-chain common-angle oxygen ejection formed by octahedron common edges, and crushing and screening to obtain the natural potassium manganese ore material with nano-aperture. The oxygen release material comprises one or any combination of two of calcium peroxide and magnesium peroxide. The additive is one or any combination of several of natural sodium bentonite, zeolite or calcium carbonate. The biochar is obtained by drying biomass and then performing anoxic pyrolysis on the dried biomass, and the biomass is one or any combination of crop straws, peanut shells, shaddock peels and coconut shells. The modified oxidative catalyst is copper-doped ultrafine zinc oxide particles. The pH buffering agent is any combination of two or more of potassium dihydrogen phosphate, potassium hydrogen phosphate, diammonium hydrogen phosphate and ammonium sulfate.
In the examples, calcium peroxide, potassium dihydrogen phosphate, ammonium sulfate, zinc acetate, sodium acetate, copper chloride, and the like were purchased from Shanghai pharmaceutical group chemical Co., Ltd; the natural manganese potassium ore is from manganese ore in a certain county in Guangxi; the additive is from Sichuan area; the corn stalks come from Shanghai Qingpu area.
The environment repairing material, the biochar, the modified ultramicro nano zinc particles and the like are prepared according to the following method.
Preparing an environment repairing material: taking 2000 g of natural potassium manganese ore, putting the natural potassium manganese ore into a ball mill for ball milling for 12 h, screening to obtain particles with the particle size of 80-150 meshes, washing the particles with water, drying the particles overnight at 80 ℃, and naturally cooling to obtain the nano natural potassium manganese ore particles. The natural potassium manganese ore particles after ball milling are subjected to BET characterization, and the specific surface area is measured to be 20.23-116.45 m2/g, and the pore diameter of the particles is measured to be 0.56-46.32 nm.
Preparing biochar: repeatedly cleaning the collected corn stalks for 5 times, washing with deionized water, and adding 3.5 mg/g-1Soaking in KOH solution for 30 h, taking out, cleaning, air-drying, putting into an oven at 50-60 ℃ for overnight drying, carrying out medium-temperature anoxic pyrolysis on the dried biomass for 3-8 h to obtain biochar, and crushing the biochar into 50-80 meshes for sealing for later use;
modified ultrafine zinc oxide particles: putting zinc acetate (0.1 mol) and sodium acetate (0.12 mol) into a ball mill, ball-milling for 15 min, and transferring the powder into a crucible when the powder is viscous and transparent; moving the crucible into a microwave oven, heating for 20 min in a limited oxygen manner, and naturally cooling in inert gas to obtain ultrafine zinc oxide particles; adding 3g of copper chloride into the ultrafine zinc oxide particles, grinding for 10 min by using a mortar, putting into a microwave oven again, heating for 10 min in an oxygen-limited mode, and naturally cooling in inert gas; then adding 50 ml of partially hydrogenated vegetable oil and isobutanol (the volume ratio of the partially hydrogenated vegetable oil to the isobutanol is 3; 2), stirring uniformly at 60-80 ℃, washing with deionized water, drying in vacuum at 80-100 ℃, and ball-milling to obtain the modified ultrafine zinc oxide particles.
Example 1
The multi-effect repair material is prepared according to the preparation proportion of 20 parts of natural potassium manganese ore particles, 35 parts of oxygen release material, 8 parts of additive, 15 parts of biochar, 5 parts of modified ultramicro zinc oxide and 17 parts of pH buffering agent.
The multi-effect composite repairing material and the calcium peroxide medicament are respectively weighed, and the adding amount of the calcium peroxide component is ensured to be 1 g/L. The two materials were placed in 50 mL of oxygen-free water, and the dissolved oxygen DO concentration of the solution was measured in a closed state at regular intervals, and the results are shown in FIG. 2. In the initial stage of oxygen release, the calcium peroxide and water react rapidly, the concentration of dissolved oxygen in water reaches nearly 6 mg/L after 10 hours, and then the dissolved oxygen in water is basically stabilized at about 6 mg/L. The oxygen release rate of the multi-effect repair material prepared by the invention at the initial stage of oxygen release is obviously lower than that of pure calcium peroxide, and the dissolved oxygen in water is about 3.5 mg/L after the multi-effect repair material reacts with the water for 10 hours; after 36 hours of reaction, the concentration of dissolved oxygen in water was about 6 mg/L. The oxygen release curve of the multi-effect repair material is more gentle than that of calcium peroxide, which shows that the multi-effect composite repair material prepared by the invention can regulate and control the oxygen release process of the oxygen release agent, reduce the waste of available oxygen and has more stable oxygen release effect.
Example 2
The multi-effect repair material is prepared according to the preparation proportion of 20 parts of natural potassium manganese ore particles, 35 parts of oxygen release material, 8 parts of additive, 15 parts of biochar, 5 parts of modified ultramicro zinc oxide and 17 parts of pH buffering agent. Weighing the multi-effect repair material and the calcium peroxide medicament, and ensuring that the adding amount of the calcium peroxide component is 1 g/L. The two materials were placed in 50 mL of oxygen-free water, and the pH change of the solution was measured in a closed condition at regular intervals, and the results are shown in FIG. 3. Calcium peroxide is added as a solution of an oxygen release agent, the pH rapidly rises to 11.0 within 10 min, and the pH reaches a stable pH of about 11.2 within 5 h. After the multi-effect repair material is added, the pH value of the solution is raised to 8.5 after 1 hour, and then the solution is basically stable and is about 8.8. The multi-effect composite repairing material buffers the pH change caused by the calcium peroxide, and reflects the excellent pH regulation and control capability of the multi-effect composite repairing material.
Example 3
The multi-effect repair material is prepared according to the preparation proportion of 20 parts of natural potassium manganese ore particles, 35 parts of oxygen release material, 8 parts of additive, 15 parts of biochar, 5 parts of modified ultramicro zinc oxide and 17 parts of pH buffering agent. The prepared multi-effect repair material is put into 100 mg/L phenol anaerobic solution, and the dosage is 5 g/L. After 24 hours of reaction, the phenol concentration and TOC in the solution were measured. The results show that the phenol removal efficiency after 24 hours reaches 95.3% and the TOC removal rate reaches 92.1%.
The multi-effect repair material is prepared according to the preparation proportion of 22 parts of natural potassium manganese ore particles, 38 parts of oxygen release material, 5 parts of additive, 10 parts of biochar, 6 parts of modified ultramicro zinc oxide and 19 parts of pH buffering agent. The prepared multi-effect repair material is put into 100 mg/L phenol anaerobic solution, and the dosage is 5 g/L. After 24 h of reaction, the phenol concentration and TOC in the solution were determined. The results show that the phenol removal efficiency reaches 100% after 24 hours, and the TOC removal rate reaches 95.7%.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (7)
1. A preparation method of a multi-effect remediation material for remediating organically-polluted underground water is characterized by comprising the following steps:
A. after ball milling, natural potassium manganese ore is put into a ball mill and screened to obtain natural potassium manganese ore particles with the particle size of 80-150 meshes, a pore structure and the pore diameter of 0.46-50.00 nm, wherein the natural potassium manganese ore adopts [ MnO [ [ MnO ]6]Double-chain common-angle oxygen jacking formed by octahedron common edges forms 2 x 2 type natural potassium manganese ore;
B. preparing biochar: cleaning biomass, soaking the biomass in a KOH solution, taking out the biomass, cleaning, air-drying the biomass, drying the biomass in an oven, performing medium-temperature anoxic pyrolysis on the dried biomass to obtain biochar, and crushing the biochar into 50-80 meshes for sealing for later use;
C. preparing modified ultramicro zinc oxide:
putting zinc acetate and sodium acetate into a ball mill for ball milling, and transferring the powder into a crucible when the powder is viscous and transparent;
secondly, moving the crucible into a microwave oven for oxygen-limited heating, and naturally cooling in inert gas to obtain ultrafine zinc oxide particles;
thirdly, adding a copper source into the ultrafine zinc oxide particles, grinding the ultrafine zinc oxide particles by using a mortar, then putting the ultrafine zinc oxide particles into a microwave oven again for oxygen-limited heating, and naturally cooling the ultrafine zinc oxide particles in inert gas;
adding partial hydrogenated vegetable oil and isobutanol, stirring uniformly, washing with deionized water, drying in vacuum, and ball-milling to obtain modified ultrafine zinc oxide particles;
D. firstly, adsorbing an oxygen release material on the surface of the biochar, and then mixing and pressing the biochar with natural potassium manganese ore particles, an additive, modified ultrafine zinc oxide particles and a pH buffering agent to form a flaky mixture;
E. calcining the flaky mixture for 4-6 h at 150-200 ℃ under the protection of inert atmosphere, cooling under the protection of inert gas, and crushing to obtain the multi-effect composite repairing material.
2. The method for preparing the multi-effect composite repairing material for repairing the organically-polluted groundwater according to claim 1, wherein in the step D, the components of the multi-effect composite repairing material for repairing the organically-polluted groundwater comprise the following components in parts by weight: 10-35 parts of natural potassium manganese ore particles, 20-45 parts of oxygen release materials, 5-18 parts of additives, 10-25 parts of biochar, 5-20 parts of modified ultrafine zinc oxide particles and 15-30 parts of pH buffering agents.
3. The method for preparing the multi-effect repairing material for repairing the organically-polluted groundwater according to claim 1, wherein in the step B, the biomass is one or any combination of several of crop straws, peanut shells, shaddock peels and coconut shells.
4. The method for preparing the multi-effect repairing material for repairing organically-polluted groundwater as claimed in claim 1, wherein the oxygen-releasing material comprises one or any combination of two of the two base materials of calcium peroxide and magnesium peroxide.
5. The method for preparing the multi-effect repairing material for repairing the organically-polluted groundwater according to claim 1, wherein the additive is one or any combination of natural sodium bentonite, zeolite or calcium carbonate.
6. The method for preparing the multi-effect repairing material for organic contaminated groundwater according to claim 1, wherein the pH buffering agent is any combination of two or more of potassium dihydrogen phosphate, potassium hydrogen phosphate, diammonium hydrogen phosphate and ammonium sulfate.
7. The preparation method of the multi-effect remediation material for organic-polluted groundwater as claimed in claim 1, wherein the prepared multi-effect composite remediation material is used for remediation of organic-polluted groundwater or remediation of organic-polluted surface water.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711459139.2A CN108249550B (en) | 2017-12-28 | 2017-12-28 | Preparation method of multi-effect remediation material for remedying organic polluted underground water |
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| CN201711459139.2A CN108249550B (en) | 2017-12-28 | 2017-12-28 | Preparation method of multi-effect remediation material for remedying organic polluted underground water |
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| CN111348715A (en) * | 2018-12-21 | 2020-06-30 | 中国人民解放军军事科学院国防工程研究院 | Multi-effect composite purifying material for purifying micro-polluted underground water and preparation method thereof |
| CN114684887B (en) * | 2020-12-30 | 2023-05-30 | 中国石油化工股份有限公司 | Petroleum-polluted underground water in-situ restoration device and method |
| CN114105331B (en) * | 2021-11-29 | 2024-04-19 | 广东省环境科学研究院 | Preparation method and application of calcium peroxide composite sustained release agent |
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